Dye mixtures

ABSTRACT

The present invention relates to dye mixtures comprising 
     (A) from 20 to 80% by weight of one or more compounds of formula (1) 
                         
wherein R 1  is C 1 -C 12 alkyl, or C 1 -C 2 alkyl interrupted by one or more oxygen atoms or —COO-groups and R 2 , R 3 , R 4  and R 5 , each independently of the others, is hydrogen, C 1 -C 12 alkyl, chlorine, bromine, hydroxy or amino and
 
(B) from 20 to 80% by weight of at least one further yellow disperse dye the sum of components (A)+(B) being 100% by weight, and to the use of those dye mixtures in the dyeing or printing of semi-synthetic or synthetic hydrophobic fiber materials.

CROSS REFERENCE TO RELATED APPLICATIONS

This application is the National Phase of International Application PCT/EP2006/062018 filed May 3, 2006 which designated the U.S. and which claims priority to European Patent Application (EP) 05104029.3 filed May 13, 2005. The noted applications are incorporated herein by reference.

The present invention relates to mixtures of anthraquinone-azo dyes and to the use thereof in the dyeing or printing of semi-synthetic or synthetic hydrophobic fibre materials.

Anthraquinone-azo dyes which, by virtue of their properties of fastness to light and to migration, can be used in a variety of pigment applications, such as, for example, in paints and in the colouring of paper and plastics, are described in EP-A 43 937.

Azo dyes based on 4-methyl-5-cyano-6-hydroxy-2-pyridones as coupling component are proposed in U.S. Pat. No. 3,640,674 for the dyeing of synthetic textile materials.

EP-A 0 601 439 discloses dye mixtures comprising at least 6 isochromatic azo dyes prepared from substituted 3-cyano-4-methylpyridines and diazo components from the aniline, aminothiophene, aminothiazole, aminoisothiazole or aminobenzisothiazole series, which exhibit virtually no temperature-dependency of the absorption behaviour and have a low tendency towards recrystallisation in dispersed form.

The anthraquinone-azo pigments based on 4-methyl-5-cyano-6-hydroxy-2-pyridones as coupling component described in U.S. Pat. No. 4,709,019 exhibit a high degree of fastness to light and to migration and are suitable especially for the colouring of plastics.

It has now, surprisingly, been found that specific mixtures comprising at least one anthraquinone-azo dye are likewise suitable for dyeing polyester fibres in the exhaust method. The dyeings obtained are distinguished by a high degree of high-temperature light fastness and by high tinctorial strength.

The present invention accordingly relates to a dye mixture comprising

(A) from 20 to 80% by weight, preferably from 25 to 60% by weight, especially from 30 to 50% by weight, of one or more compounds of formula (1)

wherein R₁ is C₁-C₁₂alkyl, or C₂-C₁₂alkyl interrupted by one or more oxygen atoms and/or —COO-groups and R₂, R₃, R₄ and R₅, each independently of the others, is hydrogen,

C₁-C₁₂alkyl, chlorine, bromine, hydroxy or amino and

(B) from 20 to 80% by weight, preferably from 25 to 60% by weight, especially from 30 to 50% by weight, of at least one compound of formulae (2)-(12)

wherein R₆ is C₁-C₁₂alkyl, or C₂-C₁₂alkyl interrupted by one or more oxygen atoms and/or —COO-groups and R₇, R₈, R₉ and R₁₀, each independently of the others, is hydrogen, C₁-C₁₂alkyl, chlorine, bromine, hydroxy or amino, with the proviso that the radical R₆ in formula (2) is different from the radical R₁ in formula (1),

-   X is the radical of a coupling component from the benzene, indene or     carbazole series, -   R₁₁ and R₁₂, each independently of the other, is Cl, Br, CF₃ or CN, -   R₁₃ is C₁-C₁₂alkyl, C₅-C₂₄aryl or C₆-C₃₀aralkyl, -   R₁₄ is H, Cl, Br or C₁-C₁₂alkyl, -   R₁₅ and R₁₆, each independently of the other, is H, Cl, Br,     C₁-C₁₂alkyl, C₁-C₁₂alkoxy or —COOR₃₃, wherein R₃₃ is C₁-C₁₂alkyl or     C₁-C₁₂alkoxy-C₁-C₁₂alkyl, -   R₁₇ is C₁-C₁₂alkyl or C₁-C₁₂alkoxy-C₁-C₁₂alkyl, -   R₁₈ and R₁₉, each independently of the other, is H, Cl, Br,     C₁-C₁₂alkyl, C₁-C₁₂alkoxy or —COOR₃₃, wherein R₃₃ is as defined     hereinabove, -   R₂₀ and R₂₁, each independently of the other, is H, Cl, Br, CF₃ or     CN or R₂₀ and R₂₁, together form a six-membered aromatic or     cycloaliphatic ring, -   Y is the radical of a diazo component of the benzene, naphthalene,     diphenyl, azobenzene, thiophene, benzothiazole, benzisothiazole,     thiadiazole, indazole, benzotriazole, pyrazole, chromone,     phthalimide or diphenylene oxide series, -   R₂₂ is H, C₁-C₁₂alkyl or C₁-C₁₂alkoxy-C₁-C₁₂alkyl, -   R₂₃ is H, Cl, Br, C₁-C₁₂alkyl, C₁-C₁₂alkoxy or —COOR₃₃, wherein R₃₃     is as defined hereinabove, -   R₂₄, R₂₅ and R₂₆, each independently of the other, is H, Cl, Br, OH,     C₁-C₁₂alkyl, C₁-C₁₂alkoxy or —COOR₃₃, wherein R₃₃ is as defined     hereinabove, -   R₂₇ and R₂₈, each independently of the other, is H, Cl, Br or     C₁-C₁₂alkyl, -   R₂₉ and R₃₀, each independently of the other, is H, Cl, Br, OH,     C₁-C₁₂alkyl, C₁-C₁₂alkoxy or —COOR₃₃, wherein R₃₃ is as defined     hereinabove, and -   R₃₁ and R₃₂ are C₁-C₁₂alkyl, C₅-C₂₄aryl or C₆-C₃₀aralkyl, -   the sum of components (A)+(B) being 100% by weight.

The dyes of formulae (1) and (2) are known, for example, from EP-A 43 937.

Any of the radicals in formulae (1)-(12) that are alkyl may be straight-chain or branched radicals.

Examples are methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, neopentyl, n-hexyl, 2-ethylhexyl, n-heptyl, n-octyl, n-nonyl, n-decyl and n-dodecyl.

Alkoxy radicals, too, may be straight-chain or branched. Examples of suitable alkoxy radicals are methoxy, ethoxy, n-propoxy, isopropoxy, tert-butoxy, n-pentyloxy, n-hexyloxy and n-decyloxy.

Aryl radicals are, for example, phenyl, tolyl, mesityl, isityl, naphthyl and anthryl.

Suitable aralkyl groups are, for example, benzyl and 2-phenylethyl.

-   C₂-C₁₂Alkyl interrupted by one or more oxygen atoms and/or     —COO-groups is, for example, 2-methoxyethyl, 2-ethoxyethyl,     2-(2-ethoxyethoxy)ethyl, —CH₂CH₂OCH₂CH₂OCH₃,     —CH₂CH₂OCH₂CH₂OCH₂CH₂OCH₃, —CH₂CH₂OCH₂CH₂OCH₂CH₂OC₂H₅,     —CH₂CH₂OCH₂CH₂OCH₂CH₂OCH₃, —CH₂CH₂OCH₂CH₂OCH₂CH₂OC₂H₅,     —CH₂CH₂COOCH₃, —CH₂CH₂COOC₂H₅, —CH₂CH₂CH₂CH₂COOCH₃,     —CH₂CH₂CH₂CH₂COOC₂H₅, —CH₂CH₂OCH₂CH₂COOCH₃ or —CH₂CH₂OCH₂CH₂COOC₂H₅.

Dye mixtures according to the invention to which preference is given comprise, as component (A), a compound of formula (1a)

wherein R₂ and R₃ are identical and are each hydrogen, chlorine or bromine and R₁, R₄ and R₅ are as defined hereinabove.

Preference is given also to dye mixtures that comprise, as component (B), a compound of formula (2a)

wherein R₇ and R₈ are identical and are each hydrogen, chlorine or bromine and R₆, R₉ and R₁₀ are as defined hereinabove.

Preferred components A are compounds of formula (1) wherein R₄ and R₅ are hydrogen or chlorine.

Preferred components B are compounds of formula (2) wherein R₉ and R₁₀ are hydrogen or chlorine.

Preference is given also to dye mixtures that comprise, as component (A), a compound of formula (1) wherein R₁ is ethyl, n-propyl, n-butyl, isobutyl, n-hexyl, 2-ethylhexyl or 3-isopropoxypropyl and R₂, R₃, R₄ and R₅ are as defined hereinabove.

Preference is given furthermore to dye mixtures that comprise, as component (B), a compound of formula (2) wherein R₆ is ethyl, n-propyl, n-butyl, isobutyl, n-hexyl, 2-ethylhexyl or 3-isopropoxypropyl and R₇, R₈, R₉ and R₁₀ are as defined hereinabove.

Suitable components (A) or (B) are, for example, the compounds of formulae (101) to (127):

The dye mixtures according to the invention comprise preferably two or three, especially two, different dyes of formula (2).

Preferred as component (A) is the compound of formula (101)

Dye mixtures to which preference is given comprise, as component (B), the compound of formula (102) and/or the compound of formula (103)

Special preference is given to dye mixtures that contain from 20 to 80% by weight, preferably from 25 to 60% by weight, especially from 30 to 50% by weight, of the compound of formula (101)

from 10 to 60% by weight, preferably from 20 to 50% by weight, especially from 25 to 40% by weight, of the compound of formula (102)

from 10 to 60% by weight, preferably from 20 to 50% by weight, especially from 25 to 40% by weight, of the compound of formula (103)

the sum of the compounds of formulae (101), (102) and (103) always being 100% by weight.

The dye mixtures according to the invention can also advantageously be used with other orange, yellow or brown dyes.

The amount of dye other than the compounds of formulae (1) and (2) is advantageously from 1 to 50% by weight, preferably from 5 to 40% by weight and especially from 10 to 30% by weight, based on the total amount of the dyes.

Preference is given to compounds of formula (3), wherein X is the radical

wherein R₂₄ and R₂₅ are 2-cyanoethyl or 2-acetoxyethyl.

Examples of suitable dyes of formulae (3) to (12) are C.I. Disperse Yellow 163, C.I. Disperse Orange 157, C.I. Disperse Orange 30, C.I. Disperse Orange 155, Dianix Yellow Brown AM-R, Dianix Yellow Brown KIS-M, C.I. Disperse Yellow 51, C.I. Disperse Yellow 65, C.I. Disperse Yellow 64, C.I. Disperse Yellow 149, Dianix Yellow AM-SLR, Dianix Orange AM-SLR, C.I. Solvent Brown 53, C.I. Solvent Yellow 97, C.I. Pigment Orange 70, C.I. Disperse Yellow 114, C.I. Disperse Yellow 71, C.I. Disperse Orange 29, C.I. Disperse Yellow 42, Disperse Yellow 86 and C.I. Solvent Yellow 163.

The dye mixtures according to the invention can be prepared in customary manner by blending the components with the aid of known mixing apparatuses (e.g. stirrers, rollers).

The dye mixtures according to the invention can be used in the dyeing and printing of semi-synthetic and, especially, synthetic hydrophobic fibre materials, especially textile materials. Textile materials of fabric blends that comprise such semi-synthetic or synthetic hydrophobic textile materials can likewise be dyed or printed using the dye mixtures according to the invention.

Semi-synthetic textile materials that come into consideration are especially cellulose 2½ acetate and cellulose triacetate.

Synthetic hydrophobic textile materials consist especially of linear, aromatic polyesters, for example polyesters of terephthalic acid and glycols, especially ethylene glycol, or condensation products of terephthalic acid and 1,4-bis(hydroxymethyl)cyclohexane; of polycarbonates, e.g. polycarbonates obtained from α,α-dimethyl-4,4′-dihydroxy-diphenyl-methane and phosgene, and of fibres based on polyvinyl chloride and on polyamide.

The dye mixtures according to the invention can be applied to the textile materials according to known dyeing methods. For example, polyester fibres materials are dyed in the exhaust method from aqueous dispersion in the presence of customary anionic or non-ionic dispersants and, optionally, customary swelling agents (carriers) at temperatures of from 80 to 140° C. Cellulose 2½ acetate is preferably dyed at from approximately 65 to 85° C. and cellulose triacetate at temperatures up to 115° C. The dye mixtures according to the invention are also suitable for use in the dyeing of polyester blends, such as, for example, polyester/cellulose fibre blends.

The dye mixtures according to the invention are suitable for dyeing in accordance with the thermosol method, in the exhaust and continuous method, and for printing processes. The exhaust method is preferred. The liquor ratio depends on the apparatus parameters, on the substrate and on the make-up, but can be selected from within a wide range, for example from 1:4 to 1:100; it is preferably, however, in the range from 1:6 to 1:25.

The said textile material can be in a variety of processing forms, such as, for example, in the form of fibres, yarns or non-wovens, in the form of woven fabrics or knitted fabrics.

It is advantageous to convert the dye mixtures according to the invention into a dye preparation prior to use. For that purpose, the dyes are so ground that their particle size is on average from 0.1 to 10 microns. Grinding may be carried out in the presence of dispersants. For example, the dried dye is ground with a dispersant or is kneaded into paste form with a dispersant and then dried in vacuo or by atomisation. The preparations so obtained can be used, after the addition of water, to prepare printing pastes and dye baths.

For printing, the customary thickeners will be used, e.g. modified or unmodified natural products, for example alginates, British gum, gum arabic, crystal gum, carob flour, tragacanth, carboxymethyl cellulose, hydroxyethyl cellulose, starch or synthetic products, for example polyacrylamides, polyacrylic acid or copolymers thereof, or polyvinyl alcohols. The dye mixtures according to the invention impart to the mentioned materials, especially to the polyester material, level colour shades having high tinctorial strength and very good in-use fastness properties, such as, especially, good fastness to light, especially very good high-temperature light fastness.

Especially good fastness-to-light properties can be achieved when the dye mixtures according to the invention additionally comprise UV absorbers.

The dye mixtures according to the invention can also readily be used together with other dyes to produce mixed shades.

The dye mixtures according to the invention are furthermore also suitable for dyeing hydrophobic fibre materials from supercritical CO₂.

The present invention relates also to the above-mentioned use of the dye mixtures according to the invention and to a method of dyeing or printing semi-synthetic or synthetic hydrophobic fibre materials, especially textile materials, which comprises applying a dye mixture according to the invention to the said materials or incorporating it therein. The mentioned hydrophobic fibre materials are preferably textile polyester materials. Further substrates that can be treated by the process according to the invention and also preferred process conditions can be found hereinabove in the more detailed explanation of the use of the dye mixtures according to the invention.

The following Examples serve to illustrate the invention. Unless otherwise indicated, parts are parts by weight and percentages are percentages by weight. The temperatures are given in degrees Celsius. The relationship between parts by weight and parts by volume is the same as that between grams and cubic centimetres.

EXAMPLE 1

100 g of polyester fabric are immersed at room temperature, at a liquor ratio of 1:20, in a liquor containing

0.5 g of the dye mixture comprising the azo dyes of formula (104), (107) and (108) in a ratio of 1:1:1,

1 g/l of ammonium sulfate and

0.5 g/l of a commercial levelling agent,

the liquor having been adjusted to a pH value of from 4.5 to 5 using 80% formic acid. The liquor is then heated first at a heating rate of 3° C./minute to 60° C. and then at a heating rate of 2° C./minute to 135° C.

At 135° C., dyeing is carried out for 60 minutes. The liquor is then cooled to 40° C., and the dyed polyester fabric is washed with water and cleaned reductively at from 70 to 80° C., for 20 minutes, in a bath containing 5 ml/l of 30% sodium hydroxide solution, 2 g/l of 85% sodium dithionite solution and 1 g/l of a commercial detergent. The finished dyeing is then washed with water and dried.

A tinctorially strong lemon-yellow dyeing having good allround fastness properties, especially high-temperature light fastness properties that are excellent, is obtained.

EXAMPLE 2

100 g of polyester fabric are immersed at room temperature, at a liquor ratio of 1:20, in a liquor containing

0.6 g of the dye mixture comprising the azo dyes of formulae (101), (102) and (103) in a ratio of 1:1:1,

1 g/l of ammonium sulfate and

0.5 g/l of a customary levelling agent,

the liquor having been adjusted to a pH value of from 4.5 to 5 using 80% formic acid. The liquor is then heated first at a heating rate of 3° C./minute to 60° C. and then at a heating rate of 2° C./minute to 135° C.

At 135° C., dyeing is carried out for 60 minutes. The liquor is then cooled to 40° C., and the dyed polyester fabric is washed with water and cleaned reductively at from 70 to 80° C., for 20 minutes, in a bath containing 5 ml/l of 30% sodium hydroxide solution, 2 g/l of 85% sodium dithionite solution and 1 g/l of a commercial detergent. The finished dyeing is then washed with water and dried.

A tinctorially strong yellow dyeing having good allround fastness properties, especially high-temperature light fastness properties that are excellent, is obtained.

EXAMPLE 3

100 g of polyester fabric are immersed at room temperature, at a liquor ratio of 1:20, in a liquor containing

0.5 g of the dye mixture comprising the azo dyes of formulae (108) and (109) in a ratio of 30:70,

1 g/l of ammonium sulfate and

0.5 g/l of a customary levelling agent,

the liquor having been adjusted to a pH value of from 4.5 to 5 using 80% formic acid. The liquor is then heated first at a heating rate of 3° C./minute to 60° C. and then at a heating rate of 2° C./minute to 135° C.

At 135° C., dyeing is carried out for 60 minutes. The liquor is then cooled to 40° C., and the dyed polyester fabric is washed with water and cleaned reductively at from 70 to 80° C., for 20 minutes, in a bath containing 5 ml/l of 30% sodium hydroxide solution, 2 g/l of 85% sodium dithionite solution and 1 g/l of a commercial detergent. The finished dyeing is then washed with water and dried.

A tinctorially strong yellow dyeing having good allround fastness properties, especially high-temperature light fastness properties that are excellent, is obtained.

EXAMPLE 4

100 g of polyester fabric are immersed at room temperature, at a liquor ratio of 1:20, in a liquor containing

0.7 g of the dye mixture comprising the azo dyes of formulae (101), (102), (103) and C.I. Solvent Yellow 163 in a ratio of 10:20:20:50,

1 g/l of ammonium sulfate and

0.5 g/l of a customary levelling agent,

the liquor having been adjusted to a pH value of from 4.5 to 5 using 80% formic acid. The liquor is then heated first at a heating rate of 3° C./minute to 60° C. and then at a heating rate of 2° C./minute to 135° C.

At 135° C., dyeing is carried out for 60 minutes. The liquor is then cooled to 40° C., and the dyed polyester fabric is washed with water and cleaned reductively at from 70 to 80° C., for 20 minutes, in a bath containing 5 ml/l of 30% sodium hydroxide solution, 2 g/l of 85% sodium dithionite solution and 1 g/l of a commercial detergent. The finished dyeing is then washed with water and dried.

A tinctorially strong yellow dyeing having good allround fastness properties, especially high-temperature light fastness properties that are excellent, is obtained.

EXAMPLES 5 TO 41

A polyester fabric is dyed with the dye mixtures indicated in Tables 1 and 2 in the manner described in Example 1. The amounts of dye are indicated in % by weight in Tables 1 and 2, the sum of the amounts of all dyes being in each case 100% by weight.

Tinctorially strong yellow dyeings having good allround fastness properties, especially high-temperature light fastness properties that are excellent, are obtained.

TABLE 1 Example 5 6 7 8 9 10 11 12 13 Compound of formula (101) 25 35 25 25 25 25 25 Compound of formula (102) 25 35 25 33 25 25 25 Compound of formula (103) 25 25 33 25 25 25 25 Compound of formula (107) 25 Compound of formula (108) 30 Compound of formula (126) 50 Compound of formula (127) 25 33 25 C.I. Solvent Yellow 163 25 50 C.I. Disperse Orange 157 25 C.I. Disperse Yellow 51 C.I. Disperse Yellow 42 25 C.I. Solvent Brown 59 25 C.I. Pigment Orange 70 Dianix Yellow AM-SLR Dianix Orange AM-SLR Example 14 15 16 17 18 19 20 21 22 Compound of formula (101) 25 25 25 25 20 10 25 Compound of formula (102) 25 25 25 25 20 20 10 25 Compound of formula (103) 25 25 25 25 20 20 10 25 25 Compound of formula (107) Compound of formula (108) 10 Compound of formula (126) Compound of formula (127) 25 C.I. Solvent Yellow 163 20 30 40 C.I. Disperse Orange 157 C.I. Disperse Yellow 51 25 20 25 C.I. Disperse Yellow 42 30 C.I. Solvent Brown 59 C.I. Pigment Orange 70 25 Dianix Yellow AM-SLR 25 35 Dianix Orange AM-SLR 25 35 Example 23 24 25 26 27 28 29 30 Compound of formula (101) 10 Compound of formula (102) 40 Compound of formula (103) 25 20 50 Compound of formula (107) 10 50 50 50 Compound of formula (108) 50 Compound of formula (126) 25 30 20 Compound of formula (127) 20 C.I. Solvent Yellow 163 25 50 30 C.I. Disperse Orange 157 50 C.I. Disperse Yellow 51 50 C.I. Disperse Yellow 42 25 50 40 30 C.I. Solvent Brown 59 C.I. Pigment Orange 70 Dianix Yellow AM-SLR 35 Dianix Orange AM-SLR 35

TABLE 2 Example 31 32 33 34 35 36 37 38 39 40 41 Comp. of formula 15 11 16 24 11 16 11 13 10 19 (101) Comp. of formula 15 11 16 24 11 16 11 13 10 15 (102) Comp. of formula 15 11 16 24 11 16 11 13 10 (103) Comp. of formula 19 (115) Comp. of formula 19 15 (117) Comp. of formula 15 (122) C.I. S YE 163 55 22 22 50 35 C.I. DS YE 65 6 6 6 C.I. DS YE 114 11 C.I. DS OR 157 25 24 46 11 16 C.I. DS YE 42 42 57 56 70 27 C.I. DS YE 64 10 C.I. DS YE 51 20 

1. A dye mixture comprising (A) from 20 to 80% by weight of one or more compounds of formula (1)

wherein R₁ is C₁-C₁₂ alkyl, or C₂-C₁₂ alkyl interrupted by one or more oxygen atoms and/or —COO— groups and R₂, R₃, R₄ and R₅, each independently of the others, is hydrogen, C₁-C₁₂ alkyl, chlorine, bromine, hydroxy or amino and (B) from 20 to 80% by weight of at least one compound of formulae (2)-(12)

wherein R₆ is C₁-C₁₂ alkyl, or C₂-C₁₂ alkyl interrupted by one or more oxygen atoms and/or —COO— groups and R₇, R₈, R₉ and R₁₀, each independently of the others, is hydrogen, C₁-C₁₂ alkyl, chlorine, bromine, hydroxy or amino, with the proviso that the radical R₆ in formula (2) is different from the radical R₁ in formula (1), X is the radical of a coupling component from the benzene, indene or carbazole series, R₁₁ and R₁₂, each independently of the other, is Cl, Br, CF₃ or CN, R₁₃ is C₁-C₁₂ alkyl, C₅-C₂₄ aryl or C₆-C₃₀ aralkyl, R₁₄ is H, Cl, Br or C₁-C₁₂ alkyl, R₁₅ and R₁₆, each independently of the other, is H, Cl, Br, C₁-C₁₂ alkyl, C₁-C₁₂ alkoxy or —COOR₃₃, wherein R₃₃ is C₁-C₁₂ alkyl or C₁-C₁₂ alkoxy-C₁-C₁₂ alkyl, R₁₇ is C₁-C₁₂ alkyl or C₁-C₁₂ alkoxy-C₁-C₁₂ alkyl, R₁₈ and R₁₉, each independently of the other, is H, Cl, Br, C₁-C₁₂ alkyl, C₁-C₁₂ alkoxy or —COOR₃₃, wherein R₃₃ is as defined hereinabove, R₂₀ and R₂₁ are H, Cl, Br, CF₃ or CN or R₂₀ and R₂₁ together form a six-membered aromatic or cycloaliphatic ring, Y is the radical of a diazo component of the benzene, naphthalene, diphenyl, azobenzene, thiophene, benzothiazole, benzisothiazole, thiadiazole, indazole, benzotriazole, pyrazole, chromone, phthalimide or diphenylene oxide series, R₂₂ is H, C₁-C₁₂ alkyl or C₁-C₁₂ alkoxy-C₁-C₁₂ alkyl, R₂₃ is H, Cl, Br, C₁-C₁₂ alkyl, C₁-C₁₂ alkoxy or —COOR₃₃, wherein R₃₃ is as defined hereinabove, R₂₄, R₂₅ and R₂₆, each independently of the other, is H, Cl, Br, OH, C₁-C₁₂ alkyl, C₁-C₁₂ alkoxy or —COOR₃₃, wherein R₃₃ is as defined hereinabove, R₂₇ and R₂₈, each independently of the other, is H, Cl, Br or C₁-C₁₂ alkyl, R₂₉ and R₃₀, each independently of the other, is H, Cl, Br, OH, C₁-C₁₂ alkyl, C₁-C₁₂ alkoxy or —COOR₃₃, wherein R₃₃ is as defined hereinabove, and R₃₁ and R₃₂ are C₁-C₁₂ alkyl, C₅-C₂₄ aryl or C₆-C₃₀ aralkyl, the sum of components (A)+(B) being 100% by weight.
 2. A dye mixture according to claim 1 comprising, as component (A), a compound of formula (1a)

wherein R₂ and R₃ are identical and are each hydrogen, chlorine or bromine and R₁, R₄ and R₅ are as defined in claim
 1. 3. A dye mixture according to claim 1 comprising, as component (B), a compound of formula (2a)

wherein R₇ and R₈ are identical and are each hydrogen, chlorine or bromine and R₆, R₉ and R₁₀ are as defined in claim
 1. 4. A dye mixture according to claim 1 comprising, as component (A), a compound of formula (1) wherein R₄ and R₅ are hydrogen or chlorine.
 5. A dye mixture according to claim 1 comprising, as component (B), a compound of formula (2) wherein R₉ and R₁₀ are hydrogen or chlorine.
 6. A dye mixture according to claim 1 comprising, as component (A), a compound of formula (1) wherein R₁ is ethyl, n-propyl, n-butyl, isobutyl, n-hexyl, 2-ethylhexyl or 3-isopropoxypropyl and R₂, R_(3, 1) and R₅ are as defined in claim
 1. 7. A dye mixture according to claim 1 comprising, as component (B), a compound of formula (2), wherein R₆ is ethyl, n-propyl, n-butyl, isobutyl, n-hexyl, 2-ethyihexyl or 3-isopropoxypropyl and R₇, R₈, R₉ and R₁₀ are as defined in claim
 1. 8. A dye mixture according to claim 1 comprising, as component (B), two or three different dyes of formula (2).
 9. A dye mixture according to claim 1 comprising, as component (A), the compound of formula (101)


10. A dye mixture according to claim 1 comprising, as component (B), the compound of formula (102) and/or the compound of formula (103)


11. A dye mixture according to claim 1 comprising from 20 to 80% by weight of the compound of formula (101)

from 10 to 60% by weight of the compound of formula (102)

from 10 to 60% by weight of the compound of formula (103)

the sum of the compounds of formula (101), (102) and (103) always being 100% by weight.
 12. A dye mixture according to claim 1 comprising, as component (B), at least one disperse dye of formula (2) and at least one disperse dye of formulae (3) to (12).
 13. A method of dyeing or printing a semi-synthetic or synthetic hydrophobic fibre material comprising applying a dye mixture to the fibre material wherein the dye mixture comprises (A) from 20 to 80% by weight of one or more compounds of formula (1)

wherein R₁ is C₁-C₁₂ alkyl, or C₂-C₁₂ alkyl interrupted by one or more oxygen atoms and/or —COO— groups and R₂, R₃, R₄ and R₅, each independently of the others, is hydrogen, C₁-C₁₂ alkyl, chlorine, bromine, hydroxy or amino and (B) from 20 to 80% by weight of at least one compound of formulae (2)-(12)

wherein R₆ is C₁-C₁₂ alkyl, or C₂-C₁₂ alkyl interrupted by one or more oxygen atoms and/or —COO— groups and R₇, R₈, R₉ and R₁₀, each independently of the others, is hydrogen, C₁-C₁₂ alkyl, chlorine, bromine, hydroxy or amino, with the proviso that the radical R₆ in formula (2) is different from the radical R₁ in formula (1), X is the radical of a coupling component from the benzene, indene or carbazole series, R₁₁ and R₁₂, each independently of the other, is Cl, Br, CF₃ or CN, R₁₃ is C₁-C₁₂ alkyl, C₅-C₂₄ aryl or C₆-C₃₀ aralkyl, R₁₄ is H, Cl, Br or C₁-C₁₂ alkyl, R₁₅ and R₁₆, each independently of the other, is H, Cl, Br, C₁-C₁₂ alkyl, C₁-C₁₂ alkoxy or —COOR₃₃, wherein R₃₃ is C₁-C₁₂ alkyl or C₁-C₁₂ alkoxy-C₁-C₁₂ alkyl, R₁₇ is C₁-C₁₂ alkyl or C₁-C₁₂ alkoxy-C₁-C₁₂ alkyl, R₁₈ and R₁₉, each independently of the other, is H, Cl, Br, C₁-C₁₂ alkyl, C₁-C₁₂ alkoxy or —COOR₃₃, wherein R₃₃ is as defined hereinabove, R₂₀ and R₂₁ are H, Cl, Br, CF₃ or CN or R₂₀ and R₂₁ together form a six-membered aromatic or cycloaliphatic ring, Y is the radical of a diazo component of the benzene, naphthalene, diphenyl, azobenzene, thiophene, benzothiazole, benzisothiazole, thiadiazole, indazole, benzotriazole, pyrazole, chromone, phthalimide or diphenylene oxide series, R₂₂ is H, C₁-C₁₂ alkyl or C₁-C₁₂ alkoxy-C₁-C₁₂ alkyl, R₂₃ is H, Cl, Br, C₁-C₁₂ alkyl, C₁-C₁₂ alkoxy or —COOR₃₃, wherein R₃₃ is as defined hereinabove, R₂₄, R₂₅ and R₂₆, each independently of the other, is H, Cl, Br, OH, C₁-C₁₂alkyl, C₁-C₁₂ alkoxy or —COOR₃₃, wherein R₃₃ is as defined hereinabove, R₂₇ and R₂₈, each independently of the other, is H, Cl, Br or C₁-C₁₂ alkyl, R₂₉ and R₃₀, each independently of the other, is H, Cl, Br, OH, C₁-C₁₂ alkyl, C₁-C₁₂ alkoxy or —COOR₃₃, wherein R₃₃ is as defined hereinabove, and R₃₁ and R₃₂ are C₁-C₁₂ alkyl, C₅-C₂₄ aryl or C₆-C₃₀ aralkyl, the sum of components (A)+(B) being 100% by weight.
 14. A semi-synthetic or synthetic hydrophobic fibre material dyed or printed according to the method of claim
 13. 